JPH02153956A - Thermoplastic resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain a composition having well-balanced physical properties by adding an epoxy group-containing copolymer and an ethylene-alpha, beta-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer to a polypropylene resin and a polyamide resin. CONSTITUTION:100 pts. wt. of a resin composition which is composed of (A) 10 to 90wt.% of a modified polypropylene or a modified polypropylene/ polypropylene composition and (B) 90 to 100wt.% of a polyamide resin are combined with (C) 2 to 30 pts. wt. of an epoxy group-containing copolymer (preferably an ethylenic copolymer), (D) 2 to 100 pts. wt. of a copolymer from 50 to 90wt.%, preferably 65 to 90wt.% of ethylene, 6 to 49wt.%, preferably 10 to 35wt.% of an alpha,beta-unsaturated carboxylic acid alkyl ester, and 0.5 to 10wt.%, preferably 1 to 2.5%of maleic anhydride to give a composition. Then, 100 pts. wt. of the composition are mixed with 5 to 100 pts. wt. of inorganic filler to give the subject composition.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel thermoplastic resin composition that can be used as a molded article, sheet, film, etc. by injection molding, extrusion molding, or the like.

More specifically, a polypropylene resin and a polyamide resin are blended with an epoxy group-containing copolymer and an ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, which has excellent physical property balance, appearance, and paintability. The present invention relates to a new thermoplastic resin composition.

<Conventional technology> Polypropylene has excellent properties such as moldability, toughness, water resistance, gasoline resistance, and chemical resistance, and is low in specific gravity and inexpensive, so it is used in various molded products and films. , has been widely used as a sheet.

However, polypropylene has some difficulties or points that need improvement in terms of heat resistance, rigidity, impact resistance, paintability, adhesion, printability, etc., and these are obstacles to the development of new practical applications. There is.

Composite polypropylene filled with rubber or reinforcing materials has been developed to improve heat resistance, stiffness, and impact strength. However, when reinforcing agents are used to improve heat resistance and stiffness, impact strength decreases significantly. , and it is not possible to obtain heat resistance higher than the melting point of polypropylene. Furthermore, blending rubber to improve impact strength results in a decrease in heat resistance and surface hardness, and it is essentially difficult to improve the balance of these physical properties with composite polypropylene.

On the other hand, polyamide resin is widely used in the fields of automobile parts and electrical/electronic parts as an engineering resin with features such as heat resistance, rigidity, strength, and oil resistance. Further improvements in water resistance, chemical resistance, etc. are desired. Furthermore, it has the inherent disadvantage that it has a higher specific gravity and is more expensive than polyolefin.

<Problems to be Solved by the Invention> From this point of view, a thermoplastic resin is created by blending a polypropylene resin selected from modified polypropylene or a modified polypropylene/polypropylene composition with a polyamide resin, and which has the features of both a polypropylene resin and a polyamide resin. If this can be achieved, the possibility of a wide range of new applications is expected. However, polypropylene resins and polyamide resins have traditionally been considered to be a combination with extremely poor compatibility and dispersibility, and in fact, simply mixing them will result in poor molten polymer balancing effect, making it impossible to take off extruded strands stably. , and the molding workability is significantly reduced. (2) Injection molded products exhibit extreme non-uniformity and have a poor appearance due to flow marks, making them practically unusable for applications such as automobile parts and electrical/electronic parts. ■In addition, the mechanical properties of molded products made from mixtures of polypropylene resin and polyamide resin, especially impact resistance and tensile elongation, are usually lower than the values expected from the additivity of the physical properties of each individual resin. There are many things to show. ■Polypropylene is originally a material with poor paintability, adhesion, and printability, so although some improvements can be made by incorporating polyamide resin, there are problems such as instability in these properties.

The object of the present invention is to provide an extremely well-balanced physical property such as excellent paintability, moldability, rigidity, heat resistance, impact resistance, scratch resistance, oil resistance, chemical resistance, and water resistance, as well as uniform appearance and An object of the present invention is to provide a new thermoplastic resin composition having excellent smoothness.

<Means for Solving the Problems> The present invention comprises 10 to 90% by weight of a polypropylene resin (8) selected from modified polypropylene or a modified polypropylene/polypropylene composition, and a polyamide resin 090 to 90% by weight.
2 to 30 parts by weight of the epoxy group-containing copolymer (C) and ethylene-α,β-unsaturated carboxylic acid alkyl ester-
A thermoplastic resin composition characterized by blending 2 to 100 of a maleic anhydride copolymer (D), and a thermoplastic resin obtained by blending an inorganic filler (E) into the composition. The present invention relates to a composition.

The polypropylene resin used in the present invention is a resin selected from modified polypropylene or modified polypropylene/polypropylene compositions.

Here, polypropylene refers to crystalline polypropylene, and includes not only propylene homopolymers but also block or random copolymers obtained by copolymerizing propylene with an a-olefin such as ethylene or butene-1.

Homopolymers, block or random copolymers of propylene can be obtained, for example, by reaction in the presence of a combined catalyst with titanium trichloride and an alkyl aluminum compound, commonly referred to as a Ziegler-Natsuta type catalyst.

In the present invention, modified polypropylene refers to such a homopolymer or copolymer of Robilev.
An unsaturated carboxylic acid or its derivative alone or in combination with an unsaturated aromatic monomer is graft-modified in the coexistence of a radical initiator.

By coexisting with an unsaturated aromatic monomer and performing graft modification, a modified polypropylene with a large amount of unsaturated carboxylic acid or its derivatives grafted, and with small changes in fluidity (melt flow rate) before and after graft modification and excellent physical properties can be obtained. can get.

In the present invention, unsaturated carboxylic acids or derivatives thereof used for graft modification to obtain the modified polypropylene include, for example, acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, citraconic acid, hymic acid, bicyclo(2,2,2)oct-5-ene-2,3-
Dicarboxylic acid, 4-methylcyclohex-4-ene-1
,2 dicarboxylic acid, 1.2.3.4.5.8.9.10
-octahydronaphthalene-2,3-dicarboxylic acid, bicyclo(2,2,1)oct-7-ene-2,3,5,
6-tetracarolebonic acid, 7-oxa-bicyclo(2,
2゜l) Hept-5-ene-2,3) unsaturated carboxylic acids such as V-boxylic acid, and derivatives of unsaturated carboxylic acids such as acid anhydrides, esters, amides, imides, and metal salts. Yes, for example, maleic anhydride, itaconic anhydride, citraconic anhydride, himic anhydride, maleic acid monoethyl ester, fumaric acid monomethyl ester, itaconic acid monomethyl ester, fumaric acid monomethyl ester, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide , acrylamide,
Methacrylamide, maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid N,N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N,N-dibutylamide, fumaric acid monoamide , fumaric acid diamide, fumaric acid-N-
Monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutyramide, fumaric acid-N,N
Examples include -dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate, and the like.

Among these, it is most preferable to use maleic anhydride.

The unsaturated aromatic monomer used in the modified polypropylene is most preferably styrene, but o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, etc.
Methylstyrene, vinyltoluene, vinylbenzene, etc. can also be used, and it is also possible to use a mixture of these.

Although the modified polypropylene can be produced in the absence of a radical initiator, it is usually preferably carried out in the presence of a radical initiator.

As the radical initiator, known ones can be used. For example, 2,2°-7zobisisobutyronitrile, 2
, 2'-azobis(2,4,4)-)limethylvaleronitrile and other azo compounds, methyl ethyl ketone peroxide, non-peroxide such as 3,3.
5-Trimethylcyclohexanone peroxide, 2
．． 2-bis(1-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisofurobyl benzene hydroperoxide, 2,5-dimethyl hemosan-2,5-cybidroba-
oxide, di-t-butyl peroxide, l,3-bis(t-butylperoxyisofurovir)benzene, 2
．． 5-dimethyl-2゜5-di(1-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di(1-butylperoxy)hexyne-3, lauroyl peroxide, 3°3.5-)IJ methylhexanoyl peroxide, benzoyl peroxide, t- Butyl peracetate, t-butylperoxyisobutyrate, t-butyloxypivalate, t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-
) Limethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2.5-dimethyl-2
, 5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylverioquine isoflovir carbonate, and polystyrene peroxide.

Various known methods can be used to graft the graft monomer onto polypropylene.

For example, one method involves mixing polypropylene, a graft monomer, and a radical generator, and grafting the mixture by melt-kneading it in a melt-kneading device. After dissolving polypropylene in an organic solvent such as xylene, the radical generator is added under a nitrogen atmosphere and the mixture is stirred. There are methods to obtain grafted polypropylene by heating, cooling after the reaction, washing and filtration, and drying, methods of irradiating polypropylene with ultraviolet rays or radiation in the presence of the graft monomer, or methods of contacting polypropylene with oxygen or ozone. be.

In consideration of economical efficiency and the like, the most preferred method is to perform graft copolymerization by melt-kneading in a melt-kneading apparatus.

Polypropylene is mixed with an unsaturated carboxylic acid or its derivative and an unsaturated aromatic monomer, if necessary in the presence of a radical initiator, at a temperature of 150 to 300°C, preferably 190 to 280°C, from 0.3 to Melt kneading can be carried out using an extruder, Banbury mixer, kneader, etc. for a residence time of 10 minutes, preferably 0.5 to 5 minutes. Industrially, single-screw and twin-screw extruders are used to keep the vent hole in a vacuum state, and produce side reactions such as unreacted components (unsaturated carboxylic acids or derivatives thereof, radical initiators, etc.) and their oligomers and decomposition products. A method of continuous production while removing substances is advantageous.The reaction atmosphere may be air, but preferably an inert gas such as nitrogen or carbon dioxide.

In addition, in order to further remove trace amounts of unreacted components and side reaction products contained in the obtained modified polypropylene, heat treatment at a temperature of 60° C. or higher, solvent extraction, and evacuation while melting are performed. You can also do that.

In addition, for modified polypropylene, antioxidants, heat stabilizers, light stabilizers, nucleating agents, lubricants, antistatic agents,
Various additives such as inorganic or organic colorants, rust inhibitors, crosslinking agents, foaming agents, lubricants, plasticizers, fluorescent agents, surface smoothing agents, surface gloss improvers, etc. are added during the manufacturing process or in subsequent processing steps. can do.

In the method for producing modified polypropylene, the melt flow rate of the raw material polypropylene (crystalline glopylev homopolymer, crystalline propylene-ethylene/Mie olefin block copolymer, crystalline flopylene-a-olefin random copolymer, etc.) is 0.05 to 60f/10min, preferably 0.1 to 40r/10min (melt flow rate of modified polypropylene prisoner obtained) KaO,1
~1002/10 minutes, preferably 0.5-59? 7
It is desirable to select a time period of 10 minutes. Also, what is the number average molecular weight of the raw material polypropylene? ,000～soo
, ooo.

Preferably it is 10,000 to 700,000.

In the method for producing modified polypropylene, the blending amount of each component is preferably 0.01 parts by weight of unsaturated carboxylic acid or its derivative per 100 parts by weight of polypropylene.
-10 parts by weight, more preferably 0.1 to 5 parts by weight, preferably 0.01 to 10 parts by weight of unsaturated aromatic monomer,
More preferably 0.1 to 5 parts by weight and a radical initiator, preferably 0 to 5 parts by weight, even more preferably 0.0 parts by weight.
The range is 0.01 to 2 parts by weight. If the amount of unsaturated carboxylic acid or its derivative added is less than 0.01 parts by weight, there will be no significant modification effect, and if it exceeds 10 parts by weight, the modification effect will reach saturation and no further significant effect will be exhibited. Otherwise, a large amount remains in the polymer as an unreacted product, causing odor or deterioration of physical properties, which is not desirable in practice. Further, if the amount of the unsaturated aromatic monomer added is less than 0.01 parts by weight, there is no significant improvement effect, and if it exceeds 10 parts by weight, no more significant effect will be exhibited. Furthermore, if the amount of the radical initiator added exceeds 5% by weight, it will not have any more significant effect on the graft reaction of unsaturated carboxylic acids or their derivatives, and the decomposition of polypropylene will increase, resulting in poor fluidity. (Melt flow rate) Changes are large, so it is not preferred in practice.

In the present invention, the polypropylene resin (2) selected from modified polypropylene or a composition of modified polypropylene and vopropylene has a melt flow rate of 0.1-
Too f /10 minutes, particularly 0.5 to 40 t/10 minutes, is suitable.

As the polyamide resin (1) in the present invention, a polyamide obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid, and a diamine can be used. Specifically, ε-caprolactam and aminocaproic acid.

Polymers such as enantholactam, 7-7 minohebbutanoic acid, 11-aminoundecanoic acid, hexamethylene diamine, nonamethylene diamine, undecamethylene diamine,
Polymers obtained by polycondensing diamines such as dodecamethylene diamine and metaxylylene diamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, cepatic acid, dodecane dibasic acid, and σ tar acid, or polymers thereof. Examples include copolymers of

Specific examples include polyamide 6, polyamide 6.6, polyamide 6.10. polyamide 11, polyamide 12,
Examples include aliphatic polyamides such as polyamide 6 and 12, aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamide, and these may be used as a mixture or copolymer of two or more of them. It can also be used as a combination.

The epoxy group-containing copolymer (C) in the present invention is a copolymer consisting of an unsaturated epoxy compound and an ethylenically unsaturated compound.

Although there is no particular restriction on the composition ratio of the epoxy group-containing copolymer (C), it is desirable that the unsaturated epoxy compound is copolymerized in an amount of 0.1 to 50% by weight, preferably 1 to 30% by weight.

The unsaturated epoxy compound is a compound having an unsaturated group copolymerizable with an ethylenically unsaturated compound and an epoxy group in the molecule.

Examples include unsaturated glycidyl esters and unsaturated glycidyl ethers represented by the following general formulas (1) and (2).

(R is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenically unsaturated bond.) (R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond, and X is -CH2- Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid, glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

Ethylenically unsaturated compounds are olefins, Jt element a2
Vinyl esters of ~6 saturated carboxylic acids, carbon number 1~
Examples include esters of saturated alcohol component No. 8 and acrylic acid or methacrylic acid, maleic esters, tutaacrylic esters, fumaric esters, vinyl halides, styrenes, nitriles, vinyl ethers, and acrylamides. It will be done.

Specifically, ethylene, propylene, butene-11 vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethyl maleate, diethyl fumarate,
Examples include vinyl chloride, vinylidene chloride, styrene, 7-crylonitrile, isobutyl vinyl ether, and acrylamide. Among these, ethylene is particularly preferred.

Epoxy group-containing copolymers can be made in a variety of ways. Both a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which the unsaturated epoxy compound is introduced as a side chain of the copolymer may be used.Manufacturing method Specifically, an unsaturated epoxy compound and ethylene are copolymerized in the presence of a radical generator at 500 to 4,000 atm and 100 to 300°C in the presence or absence of an appropriate solvent and chain transfer agent. A method in which an unsaturated epoxy compound and a radical generator are mixed with polypropylene and melt-graft copolymerized in an extruder, or an unsaturated epoxy compound and an ethylenically unsaturated compound are mixed in an inert solvent such as water or an organic solvent. Examples include a method of copolymerizing in a solvent in the presence of a radical generator.

In the present invention, the ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer Ω means that the monomer components are (a) ethylene, (b) α,β-unsaturated unsaturated carboxylic acid. It is a copolymer consisting of arsulester (C) maleic anhydride, and (a) ethylene is 50 to
90% by weight, preferably 65-90% by weight, (b) α,
6-49% by weight of β-unsaturated carboxylic acid alkyl ester, preferably 10-35% by weight and 4c) 0.5-10% by weight of maleic anhydride, preferably 1.0-2.
It is 5% by weight.

(b) α, β-, β-carboxylic acid alkyl ester is
Alkyl esters of unsaturated carboxylic acids having 3 to 8 carbon atoms, such as acrylic acid and methacrylic acid; specific examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-acrylate. butyl,
t-Butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylate
propyl, isopropyl methacrylate, methacrylic acid n
-butyl, isobutyl methacrylate, etc. Among these, methyl acrylate, ethyl acrylate,
Preferred are n-butyl acrylate and methyl methacrylate.

Also included are ethylene copolymers obtained by copolymerizing other copolymerizable monomer components, such as vinyl acetate and vinylpepropionate, within a range that maintains performance.

In the component 0 copolymer used in the present invention, when (a) ethylene is less than 50% by weight, when the composition of the present invention is made, favorable results are obtained in terms of cold resistance, particularly impact resistance at low temperatures, and moldability. I can't get it. Moreover, if it exceeds 95% by weight, the compatibility with the polyamide resin will decrease and the paintability will also be poor.

It also has a negative effect on the impact resistance and appearance of the molded product. In addition, if (b) α,β-unsaturated carboxylic acid alkyl ester is less than 6% by weight, paintability and impact resistance at low temperatures will decrease, and if it exceeds 49% by weight, cold resistance, especially resistance at low temperatures. No favorable results are obtained in terms of impact properties. Also,
(C) Maleic anhydride is less than 0.5% by weight, or 10
If it exceeds % by weight, the cold resistance, especially the impact resistance at low temperatures, will decrease, and furthermore, it will have a negative effect on the molding processability and the appearance of the molded product.

Melt index of the copolymer 0 (JISK 676
0.190° C.) is in the range of o, i to 200 r/10 min, preferably 0.5 to 1 oof/10 min. If the melt index is less than 0.11/10 minutes, the molding processability and the uniformity of the appearance of the molded product will deteriorate, and if it exceeds 200 f/10 minutes, the mechanical properties will deteriorate, which is not preferable.

In the thermoplastic resin composition according to the present invention, the polypropylene resin holes as the first component are contained in an amount of 10 to 90% by weight, preferably 20 to 80% by weight. If the polypropylene resin (E) is less than 10% by weight, moldability, toughness, water resistance, chemical resistance, etc. will be insufficient, and if it exceeds 90% by weight, heat resistance, strength and rigidity will be poor. No desirable properties can be obtained.

When a modified PP propylene/polypropylene composition is used as the first component, it is necessary that the modified polypropylene is contained in the composition in an amount of 5% by weight or more. If it is less than 5% by weight, there will be problems with the compatibility and dispersibility of the final resin composition.
Sufficient toughness and impact resistance cannot be obtained.

The polyamide resin (2) as the second component is contained in an amount of 90 to 10% by weight, preferably 80 to 20% by weight.

If the polyamide resin (E) is less than 10% by weight, heat resistance, rigidity, strength, etc. are insufficient, and if it exceeds 90% by weight,
Favorable properties such as moldability, toughness, water resistance, and chemical resistance cannot be obtained. In terms of paintability, fluidity during molding, etc., it is more preferable that the polyamide resin has a number average molecular weight of 15,000 or less (relative viscosity of 2.4 or less).

In the present invention, the epoxy group-containing copolymer (C) is
~30 parts by weight, preferably 3 to 20 parts by weight.

If the amount is less than 2 parts by weight, there will be problems in the compatibility and dispersibility of the resin composition, the toughness and impact resistance will be insufficient, flow marks will occur, and the appearance will be unfavorable. Also, the extrusion stability is not good.

If it exceeds 30 parts by weight, layer delamination will occur in the molded product, and the rigidity and
Toughness, impact resistance, etc. deteriorate significantly, and favorable results cannot be obtained.

Furthermore, copolymer 0 is 2 to 100 parts by weight of copolymer
100 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight. If it is less than 2 parts by weight, the effect of improving paintability is poor, and if it exceeds 100 parts by weight, it is not preferable because heat resistance and rigidity are lowered.

In addition, when blending an inorganic filler (E), (A), 03
).

(C), 5 to 1 per 100 parts by weight of the composition consisting of 0
00 parts by weight, preferably 10 to 60 parts by weight. The inorganic filler (2) preferably has an aspect ratio (ratio of the major axis to the minor axis of the filler) of 5 or more, preferably 10 or more in order to improve rigidity and heat resistance.

More preferably, the inorganic filler is a plate-shaped filler such as talc or mica, and preferably has an average particle size of 4 μm or less. If the average particle size exceeds 4 μm, impact strength decreases, which is not preferable.

In addition to the above formulations, the resin composition of the present invention also contains organic fillers, reinforcing agents, whiskers, silica, alumina,
CaCO3, other fillers, pigments such as TlO2 and carbon black, flame retardants such as 5bzOs, lubricants, nucleating agents, plasticizers, dyes, antistatic agents, antioxidants, weather resistance agents, etc. are added. May be used.

There are no particular limitations on the method for producing the resin composition of the present invention,
Commonly known methods can be used.

Methods of mixing in a solution state and evaporating the solvent or precipitating in a non-solvent are also effective, but from an industrial standpoint, a method of kneading in a molten state is actually used. For melt-kneading, commonly used kneading devices such as Bamba's J-mixer, extruder, roll, and various kneaders can be used.

When mixing, it is preferable to uniformly mix each resin component in the form of powder or pellets in a device such as a tumbler or Henschel mixer, but if necessary, mixing can be omitted and the mixing device or Separate metering methods can also be used.

The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but the present invention also allows tri-blending to be performed during injection molding or extrusion molding without going through the kneading process in advance. It also includes a method of directly kneading the molded article during the melt processing operation.

There is no particular restriction on the order of crosstalk in the present invention, and ^(E3)(C)
Although 1(D) may be kneaded all at once, it is preferable to melt and knead 1 and 2 in advance, and then mix (A), (C), and (C).
A good method is to knead jl.

<Examples> The present invention will be described below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto. In addition, the tensile test in the examples is JIS K7113G:, bending test (jj 3.2 m +) jj JIS K7203 i
This was carried out accordingly. Izotsu impact strength (thickness 3.2
m) is the test result according to JIS K7110.

The modified polypropylene and epoxy group-containing copolymer used in the present examples and comparative examples were obtained by the following formulation. Commercially available polypropylene and polyamide resins were used.

(2) Modified Boga' propylene (1) Produced with reference to the method described in Japanese Patent Publication No. 56-9925.

Polypropylene, maleic anhydride and tert-butyl peroxylaurate were premixed. Scree diameter 30mm, L/D28 extruder, barrel temperature 230mm
℃, the above mixture was supplied from a hopper, and the extruder reaction was carried out at a scree rotation speed of 6 Or, p, m, and the molten modified polypropylene strand discharged from the die of the extruder was pelletized after cooling with water. The amount of maleic anhydride grafted in the obtained product was 0.08%, and the melt flow rate was 30 t710 minutes.

■Modified polypropylene (2) Polypropylene, maleic anhydride, styrene, 1,3-
Bis(1-butylperoxyisoglobil)benzene was mixed in advance, and the other procedures were the same as in modified polypropylene (1). The amount of maleic anhydride grafted was 0.15% by weight, and the melt flow rate was 25 f /IQ min.

■Polypropylene 0 Propylene homobolymer 2 Sumitomo Norphelene W2O3 made by Sumitomo Chemical Co., Ltd. Propylene-ethylene/propylene block copolymer: Sumitomo Noprene AW564 made by Sumitomo Chemical Industry ■Polyamide resin nylon 6: Unitika Nylon made by Unitika 1020BRL1025BRL 1030BRL Nylon 66: Ube Nylon 66 2020B manufactured by Ube Industries ■ Copolymer containing engineered poxy group 0 glycidyl methacrylate ethylene copolymer, glycidyl methacrylate ethylene-vinyl acetate copolymer JP-A-47-23490, JP-A-48 -1138
It was produced with reference to the method described in Publication No. 8.

Using a 40-ton stainless steel reactor equipped with appropriate supply and outlet ports and a stirrer and capable of temperature control, glycidyl methacrylate, ethylene, vinyl acetate, radical initiator, and chain transfer agent were continuously supplied. Copolymerization was carried out under conditions of 1,400 to 1,600 atm and 180 to 200° C. while stirring.

O-glycidyl methacrylate grafted ethylene-vinyl acetate copolymer was produced by referring to the method described in, for example, Japanese Patent Publication No. 12449/1983.

Glycidyl methacrylate in which dicumyl peroxide had been dissolved in advance was mixed with ethylene-vinyl acetate copolymer pellets, and the mixture was allowed to diffuse and permeate at room temperature. Next, the glycidyl methacrylate-impregnated pellets were extruded using an extruder with a 65-φ pent at a tip temperature of 170° C. to obtain graft-copolymerized epoxy group-containing copolymer pellets.

■Ethylene Copolymer Among the ethylene copolymers described below, Bondine 0 can be produced by the method described in French Patent No. 1323379 and French Patent Application No. 81/01430.

Bondine 0X8040 (E/EA/MAR=72.8/26/1.2% by weight, manufactured by Sumika CPF■)
MI: 92/10 minutes) Bondine 0X8030 (E/EA/MAH=87.5/10/2.5% by weight, manufactured by Sumika CPF■)
M I: 4.4 P/lo min) Bondine 0X4110 (E/EA/MAH=91.8515.0/3.15% by weight) manufactured by Sumika CPF ■ Bondine 0X806 manufactured by Sumika CDF ■
0 (E/EA/MAR=90.7/26/3.3% by weight)
Acrift 0 WA3036-04 (E/MMA=70/30% by weight, MI: 59/10 minutes) manufactured by Sumiya Chemical Industry ■, where E: ethylene, EA: ethyl methacrylate,
MAH: maleic anhydride.

MMA: Indicates methyl methacrylate.

■Inorganic filler: Talc MW 5000 S average particle size 3 μm manufactured by Hayashi Kasei ■ Mica manufactured by Kuraray ■ Kuraray Mica@325HK Average particle size 30 μm Mica manufactured by Wand Kogyo ■ Average particle size of Super Bite 2.7 μm Example 1 Materials shown above After blending with the composition shown in Table 1, it was heated to 26°C using a twin-screw kneader (TEX-44 manufactured by Japan Steel Works).
After melting and mixing at 0°C, it was cooled and pelletized, dried at 120°C for 4 hours, and molded using an injection molding machine with a pressure of 150 tons (Toshiba l51).
50E-V type), molding temperature 260℃, mold temperature 80℃
A test piece for measuring physical properties was prepared. The results of the test pieces obtained were as shown in Table 1. In addition, the evaluation of paint adhesion was performed using acrylic urethane paint Soflex #530 as the paint.
0 (manufactured by Kansai Paint ■), Plugloss K as primer
1100 (manufactured by NOF ■), the initial adhesion was measured after baking at 80° C. for 30 minutes.

Comparative Example 1 In Example 1, the composition was changed to the one shown in Table 1,
The rest was the same as in Example 1. The results are shown in Table 1.

Example 2 In Example IG, the composition was a combination of modified polypropylene and unmodified homopolypropylene (Jinnoblen W501, manufactured by Sumitomo Chemical Co., Ltd.) as shown in Table 1.
The rest was the same as in Example 1. The results are shown in Table 1.

Example 3 In Example 1, modified polypropylene (2) was used instead of modified polypropylene (1), and the other conditions were the same as in Example 1. The composition and results are shown in Table 1.

As seen in Examples 1 to 3 and Comparative Example 1, when a polyethylene copolymer is used, the heat resistance and flexural modulus do not change much, the impact strength improves, and surprisingly, the paintability improves. We found that there was a significant improvement in

In the composition of Comparative Example 1, the paintability of polypropylene alone is better than that of the composite polypropylene material.

However, the adhesion of the paint was unstable, forcing the use of a primer made for polypropylene, and pretreatment such as chlorocene treatment was also required, which caused problems in the painting process.

The primers used in Examples 1 and 2 and Comparative Example 1 are widely used for nylon and polyester, and are easy to handle in the coating process. The results shown in Table 1 were obtained using only a simple pretreatment such as degreasing with isopropyl alcohol.

Example 4 In Example 1, when granulating the compounding ratio shown in Table 2, pre-blended talc (MW5000S) was prepared from the first hopper.

Manufactured by Hayashi Kasei ■, average particle size 3.0μ, average aspect ratio 10
) and nylon 6 (Unitika Nylon 6゜1025BRL
, number average molecular weight 14,000), ventro and the first
The procedure was the same as in Example 1 except that the remaining preblended raw materials were charged into the second hopper provided with an intermediate stand of the hopper (the composition was controlled using a gravimetric feeder descendant), and the mixture was melted and kneaded. The results are shown in Table 2.

Example 5 In Example 4, mica (Wand Kogyo ■) was used instead of talc.
Manufactured by Super Bite, average particle size 2.7μ.

The average aspect ratio was 20), and the other conditions were the same as in Example 3.

Comparative Example 2 In Example 5, each raw material was pre-blended at once and fed from the first hopper, but the other conditions were the same as in Example 4 (strained).

Comparative Example 3 In Example 5, Mica (Superbaite) was replaced with Mica (Tin Olide Mica 325HK manufactured by Kuraray).
, an average particle diameter of 40p, and an average aspect ratio of 15) were used, and the other conditions were the same as in Example 4.

The compositions and results of Examples 4 and 5 and Comparative Examples 2 and 3 are shown in Table 2.

From the results of Examples 4 and 5 and Comparative Examples 2 and 3, it is surprising that the method of first melting and kneading the nylon and filler and then melting and kneading the remaining raw materials improved the flexural modulus, impact strength,
H, D, and T were all good.

Furthermore, although mica having a large average particle diameter tends to improve the bending modulus, it is undesirable because it causes a significant decrease in impact strength.

Example 6 In Example 5, the formulation shown in Table 3 was used, and the other conditions were the same as in Example 5.

Comparative Examples 4 to 6 In Example 6, the polyethylene copolymer was replaced with Bondine AX8040 (E/EA/MAR=7
2.8/26/1.2% by weight), and Comparative Example 4 used bonder (
LX4110 (E/EA/MAR=91.8515.
0/3.15Ii amount%), Comparative Example 5 is Bondine@TX
8030 (E/EA/ MAR= 87.5/10/
2.5% by weight), Comparative Example 6 is Acrift WA3036
-04 (E/MMA=70/30% by weight), and the same procedure as in Example 6 was repeated.

The paint adhesion results of Example 6 and Comparative Example 4.5.6 are shown in the third example.
Shown in the table.

As is clear from this, if the content of α,β-unsaturated carboxylic acid alkyl ester components such as EA and MMA in the polyethylene copolymer is less than 6M%, paint adhesion will be poor, and more preferably , 10% by weight or more.

Example 7 In Example 4, the formulation was as shown in Table 4,
The rest was the same as in Example 4.

Comparative Example 7 In Example 7, Eyelift'WA3036-04, which does not contain maleic anhydride, was used as the polyethylene copolymer, but the rest was the same as in Example 7.

Example 8 In Example 7, Bondine@AX80604E/EA/MAH=90.7/2 was used as the polyethylene copolymer.
6/3.3% by weight), and the rest was the same as in Example 7.

The results of Example 7.8 and Comparative Example 7 are shown in Table 4. As is clear from this, as a polyethylene copolymer,
Without maleic anhydride, impact strength is reduced. Further, from the viewpoint of melt fluidity, it is not preferable to have a high content of maleic anhydride.

Example 9 In Example 4, the formulation was as shown in Table 5, and the other conditions were the same as in Example 4.

Comparative Example 8 In Example 9, the epoxy group-containing copolymer was eliminated,
The other compounding ratios were as shown in Table 5, and the rest was the same as in Example 9.

The results of Example 9 and Comparative Example 8 are shown in Table 5.

If the epoxy group-containing copolymer is not included, heat resistance will decrease,
This is not good because it causes a decrease in impact strength, a decrease in flexural modulus, and a decrease in all physical properties.

Examples 10 to 12 In Example 4, the molecular weight of polyamide 6 was changed to Example 1O.
is polyamide 6, Unitika nylon 1020 (number average molecular weight 12,000, relative viscosity 2.05), Example 11 is Unitika nylon 1025 (number average molecular weight 1
4,000, relative viscosity 2.3), and Example 12 was Unitika Nylon 1030BRL (number average molecular weight 17,500).
, relative viscosity 2.6), the blending ratio was as shown in Table 6, and the other conditions were the same as in Example 4.

The results of melt fluidity (melt flow rate) are also shown in Table 6. As is clear from this, when the molecular weight becomes large, the fluidity decreases, which is not preferable.

Preferably, the number average molecular weight is 15,000 or less.

In addition, the relative viscosity of nylon 6 is the polymer concentration lf/10
Measured at 0 tut, 96% H2SO4, 25°C, and the number average molecular weight was determined by the terminal quantitative method.

<Effects of the Invention> As described above, the thermoplastic resin composition of the present invention has good molding processability, has excellent balance of physical properties of molded products, especially in terms of paintability, and has excellent impact strength, heat resistance,
It can be seen that a remarkable effect is exhibited in that the flexural modulus is well balanced.

The novel thermoplastic resin composition provided by the present invention is
Molded products, films, and
Processed into sheets, etc., it provides an excellent product with an extremely good balance of physical properties such as heat resistance, paintability, impact strength, and flexural modulus, and is used for applications in the automobile, electrical, and electronic fields.

Claims (11)

[Claims] (1) 10 to 90% by weight of polypropylene resin (A) selected from modified polypropylene or modified polypropylene/polypropylene composition and 90 to 90% by weight of polyamide resin (B)
For 100 parts by weight of a resin composition consisting of 10% by weight,
It is characterized by containing 2 to 30 parts by weight of an epoxy group-containing copolymer (C) and 2 to 100 parts by weight of an ethylene-α,β unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (D). A thermoplastic resin composition. (2) A thermoplastic resin composition comprising 5 to 100 parts by weight of an inorganic filler (E) based on 100 parts by weight of the composition according to claim 1. (3) Claim 1, wherein the epoxy group-containing copolymer (C) is a copolymer consisting of an unsaturated epoxy compound and ethylene, or a copolymer consisting of an unsaturated epoxy compound, ethylene, and an ethylenically unsaturated compound other than ethylene. The thermoplastic resin composition described. (4) Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (D) contains (a) 50 to 90% by weight of ethylene, (b) α,β-unsaturated carboxylic acid alkyl ester 6 The thermoplastic resin composition according to claim 1, which is a copolymer containing -49% by weight and (c) 0.5-10% by weight of maleic anhydride. (5) Ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (D) contains (a) 65 to 90% by weight of ethylene, (b) 10 α,β-unsaturated carboxylic acid alkyl ester 2. The thermoplastic resin composition according to claim 1, which is a copolymer containing -35% by weight and (c) 1.0-2.5% by weight of maleic anhydride. (6) The thermoplastic resin composition according to claim 2, wherein the inorganic filler (E) is talc or mica. (7) Claim 6, wherein the average particle size of the talc is 0.4μ or less.
The thermoplastic resin composition described. (8) The thermoplastic resin composition according to claim 2, wherein the inorganic filler (E) is a filler having an average aspect ratio of 5 or more. (9) Polyamide resin (B) has a number average molecular weight of 15.0
The thermoplastic resin composition according to claim 1, which is a polyamide resin having a relative viscosity of 0.00 or less (relative viscosity of 2.4 or less). (10) The thermoplastic resin composition according to claim 1, wherein the modified polypropylene (A) is a modified polypropylene obtained by graft modification of an unsaturated carboxylic acid or its derivative alone or in combination with an unsaturated aromatic monomer. . (11) In the method for obtaining a thermoplastic resin composition according to claim 2, the polyamide resin (B) and the inorganic filler (E
) is first melt-kneaded, then polypropylene resin (A
), epoxy group-containing copolymer (C) and ethylene-α
, a β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer (D) is melt-kneaded.